Use of cross-linked cationic polymers in cosmetics

ABSTRACT

The invention relates to the use of a cationic crosslinked polymer which is preparable by free-radical polymerization in the presence of salts and of protective colloids in cosmetics.

The present invention relates to a process for the preparation ofaqueous dispersions of crosslinked cationic water-soluble orwater-swellable polymers based on monoethylenically unsaturated monomerswhich contain a quaternized or quaternizable nitrogen atom, byfree-radical polymerization in an aqueous salt solution in the presenceof a protective colloid, and to their use in hair cosmetic formulations.

Cationic polymers are used as conditioning agents in cosmeticformulations. Requirements for hair conditioning agents are, forexample, a marked reduction in the required combing force in wet andalso in dry hair, good detangling upon first combing and goodcompatibility with further formulation components. Furthermore, cationicpolymers prevent electrostatic charging of the hair.

In shampoos, primarily cationic cellulose derivatives(polyquaternium-10) or guar gum derivatives are used. However, abuild-up effect is observed with these compounds, i.e. the hair becomescoated with the conditioner upon repeated use and feels weighed down.

For the conditioning and setting of keratin substances, such as hair,nails and skin, synthetic polymers have also been used for years. Inaddition, synthetic polymers are used in cosmetic formulations whichcomprise pigments or cosmetically active components, as compatibilitypromoters for achieving a homogeneous, stable formulation.

For example, copolymers of acrylamide and dimethyldiallylammoniumchloride (polyquaternium 7) are used. However, these have thedisadvantage of high residual monomer contents since acrylamide anddimethyldiallylammonium chloride have unfavorable copolymerizationparameters.

Despite extensive efforts, there continues to be a need for improvementwith polymers for producing elastic hairstyles with simultaneouslystrong hold even under high atmospheric humidity, good ability to bewashed out and good feel of the hair. The need for improvement likewiseconsists in the case of polymers for producing readily combable,detanglable hair and for conditioning skin and hair, in their sensorilyperceivable properties, such as feel, volume, handleability, etc. Inaddition, clear aqueous preparations of these polymers are desired whichare accordingly characterized by good compatibility with otherformulation constituents.

Furthermore, there is a need for polymers which are suitable asconditioning agents for cosmetic preparations and which can be preparedwith a high solids content. Of particular interest are polymers whichhave a high solids content, have a low viscosity whilst simultaneouslyretaining the application properties (such as, for example,combability).

It is an object of the present invention to find a cationic conditioningagent for cosmetic preparations, in particular shampoos, which does nothave the disadvantages mentioned.

Further quaternized polymers and their use as conditioning agents inhaircare formulations are known.

Thus, for example, EP-A-0 246 580 describes the use of uncrosslinkedhomopolymers and copolymers of 3-methyl-1-vinylimidazolium chlorides incosmetic compositions. EP-A-0 544 158 and U.S. Pat. No. 4,859,756 claimthe use of uncrosslinked homopolymers and copolymers of chloride-free,quaternized N-vinylimidazoles in cosmetic preparations. EP-A-0 715 843discloses the use of uncrosslinked copolymers of a quaternizedN-vinylimidazole, N-vinylcaprolactam and N-vinylpyrrolidone, andoptionally a further comonomer in cosmetic preparations.

DE-A-31 06 974 describes a hair treatment composition of thepreshampooing type which comprises uncrosslinked homopolymers andcopolymers of quaternized diallylammonium compounds. DE-A-28 21 239(U.S. Pat. No. 4,348,380) describes copolymers of quaternizeddiallylammonium compounds in hair cosmetic preparations. U.S. Pat. No.5,275,809, EP-A-0 522 755, EP-A-0 521 665 and EP-A-0 521 666 disclosecopolymers with dimethyldiallylammonium chloride for use in shampoos. Innone of the abovementioned specifications is a crosslinked polymerdescribed.

In addition, crosslinked cationic copolymers and their use aswater-soluble and water-insoluble additives in very diverse areas arealso described.

U.S. Pat. No. 4,806,345 describes crosslinked cationic thickeners forcosmetic formulations of quaternized dimethylaminoethyl methacrylate andacrylamide.

WO 93/25595 describes crosslinked cationic copolymers based onquaternized dialkylaminoalkyl acrylates or dialkylaminoalkylacrylamides.A proposed application is the use of these crosslinked copolymers asthickeners in cosmetic preparations.

DE-A-32 09 224 describes the preparation of crosslinked polymers basedon N-vinylpyrrolidone and (quaternized) N-vinylimidazole. These polymersare claimed for use as adsorbents and ion exchangers.

Crosslinked, agglomerated vinylimidazole copolymers are specified in WO96/26229 as dye transfer inhibitors. They are highly crosslinked,water-insoluble, barely swellable and therefore unsuitable for cosmeticformulations.

WO 96/37525 describes the preparation of crosslinked copolymers of,inter alia, N-vinylpyrrolidone and quaternized vinylimidazoles in thepresence of polymerization regulators and their use, in particular indetergents.

U.S. Pat. No. 4,058,491 discloses crosslinked cationic hydrogels ofN-vinylimidazole and N-vinylpyrrolidone and a quaternized basicacrylate, and further comonomers. These gels are proposed for thecomplexing and controlled release of anionic active substances.

DE-A-42 13 971 describes copolymers of an unsaturated carboxylic acid,quaternized vinylimidazole and optionally further monomers and acrosslinker. The polymers are proposed as thickeners and dispersants.

The use of copolymers with an aminoalkyl (meth)acrylate in cosmetics isdescribed in EP-A-0 671 157. The polymers mentioned there are, however,used exclusively for the combined application with setting orconditioning polymers.

WO 97/35544 describes the use of crosslinked cationic polymers withdialkylaminoalkyl (meth)acrylates or dialkylaminoalkyl(meth)acrylamidesin shampoo compositions.

EP-A-0 893 117 and EP 1064924 describes the use of high molecular weightcrosslinked cationic polymers as solution polymers. These have a goodconditioning effect in shampoos.

DE-A-197 31 907 describes the use of crosslinked cationic copolymerswhich contain N-vinylimidazoles in hair cosmetic formulations.

A disadvantage of these abovementioned inventions is that thepreparation of these polymers takes place in the form of solutions witha very low solids content because otherwise the viscosities of thesesolutions are too high. An additional disadvantage is the generation ofa relatively large proportion of undissolved gel particles. This leadsto a large number of application disadvantages, such as, for example,longer polymerization times, prolonged filtration and bottling times.Due to the low solids content, high costs arise during the prepartion(reactor capacities) and high transportation costs. The gel particlesproduce application disadvantages. An undesired structure in the flowbehavior of the shampoo formulation may be observed.

An alternative possibility is the use of a process for the preparationof water-soluble or water-swellable polymers in a W/O emulsion. This isclaimed in EP-A-0 126 528 and comprises polymerizing the water-solublemonomers in the presence of emulsifiers with the addition of a specialdispersion system consisting of alkanols. Use is also made inter alia ofcationic comonomers. The oil phase used is aliphatic and aromatichydrocarbons or higher aliphatic esters. The polymers are not intendedfor cosmetics applications.

The preparation of such polymers takes place according to the prior artby free-radical homopolymerization or copolymerization in either ahomogeneous or heterogeneous phase. However, homogeneous solutionpolymerization leads, even in the case of low polymer concentrations, tohigh viscosities which, due to poor space-time yields, leads to highproduction costs. Polymerization in heterogeneous phase, such as, forexample, polymerization in W/O emulsion in an organic solvent, mayproduce higher solids contents but with the disadvantage that an organicsolvent is used which is undesired for cosmetic preparations forecological and toxicological reasons. The disadvantages of apolymerization in heterogeneous phase using an organic solvent can becircumvented by preparing aqueous dispersions of water-soluble polymers.

An overview of aqueous dispersions of cationic polymers is given, forexample, in WO 98/14405 and WO 98/31748.

In many embodiments, salts are used in order to precipitate out thepolymers formed (WO 98/14490). The precipitated polymer is thenstabilized with a suitable protective colloid. Without the correspondingprotective colloid, the precipitated polymers have a tendency to sticktogether and to form a mass which is difficult to handle. Ideally, theend product should be an aqueous dispersion of a water-soluble orwater-swellable cationic polymer which has a low viscosity despite ahigh solids content.

WO 99/46207 describes, for example, the preparation of an aqueousdispersion of a high molecular weight cationic polymer. Salts orcombinations of salts are likewise used as cationic protective colloids.

Water-in-water emulsions of cationic acrylates and acrylamides in thepresence of salts are described in EP 637 581. Here, use is made ofcationic homopolymers or copolymers of cationic and neutral monomers asprotective colloids.

WO 98/14490 describes cationic polymers or copolymers of cationic andneutral monomers or copolymers of neutral and anionic monomers forincreasing the stability of emulsions.

WO 98/31748 describes the preparation of aqueous dispersions ofuncrosslinked cationic water-soluble copolymers based ondimethylaminoethylmethacrylamide (DMAEMA) and diallydimethylammoniumchloride (DADMAC) and neutral monomers such as acrylamide. For thestabilization, polyethylene glycol and polyamines are used.

WO 98/14405 describes suspensions of uncrosslinked water-solublecopolymers by polymerization of cationic methacrylamides and hydrophobicmonomers using cationic polymers as protective colloid.

Further uncrosslinked aqueous dispersions of cationic polymers aredescribed in DE 198 51 024 A1 and in WO 97/30094.

WO 99/46207 describes the preparation of aqueous dispersions ofuncrosslinked high molecular weight amphoteric polymers which arecarried out by copolymerization of anionic and cationic monomers in thepresence of cationic or anionic protective colloids. In all of theexamples mentioned, the polymerizations were carried out in the presenceof salts.

U.S. Pat. No. 6,019,904 describes a process for the deinking of paperusing a cationic polymer which is prepared in the presence of salt and aprotective colloid (dispersant).

WO 02/34796 describes a preparation process for aqueous dispersions ofpolymers in the presence of protective colloids and one or more salts,the salt being added in two or more portions during the polymerization.

It is an object of the present invention to provide a polymerizationprocess with improved space-time yields for preparing crosslinkedcationic polymers with a high molecular weight. In addition, it is anobject of the present invention to reduce the proportions of gelparticles in order to thereby eliminate an undesired structure in thecosmetic formulation.

The aqueous dispersions preparable thereby have a high solids contentand also readily handleable viscosities, are free from gel particles andare therefore highly suitable for hair cosmetic applications, forexample as conditioner.

The cationic crosslinked polymers used according to the invention areobtainable by free-radically initiated polymerization of

-   a) 1 to 99.9% by weight, based on the total amount of monomers used    for the preparation of the polymer, of at least one cationic or    cationogenic vinyl group-containing monomer chosen from the group    consisting of N-vinylimidazoles, diallylamines,    dialkylaminoalkyl(meth)acrylamides and    dialkylaminoalkyl(meth)acrylamides and dialkylaminoalkyl    (meth)acrylates,-   b) 0 to 99% by weight, based on the total amount of monomers used    for the preparation of the polymer, of at least one neutral or basic    water-soluble monomer different from (a),-   c) 0 to 50% by weight, based on the total amount of monomers used    for the preparation of the polymer, of at least one unsaturated acid    or one unsaturated anhydride,-   d) 0 to 50% by weight of at least one free-radically copolymerizable    monomer different from (a), (b) or (c), and-   e) 0.1 to 10% by weight, based on the total amount of monomers used    for the preparation of the polymer, of at least one crosslinking    monomer with at least two ethylenically unsaturated, nonconjugated    double bonds,    where the amounts a) to e) are chosen such that the resulting    polymer, optionally after quaternization or protonation, has an    overall positive charge,    in water in the presence of-   f) 1 to 100% by weight of the saturation amount in the reaction    medium of one or more organic or inorganic salts, and-   g) 0.1 to 30% by weight, based on the total weight of the    dispersion, of at least one water-soluble protective colloid with a    composition different from a) to e), and    subsequent at least partial quaternization for cases where the    monomer (a) is not quaternized.

Suitable monomers (a1) are chosen from one of the following groups:

-   -   N-vinylimidazole derivatives of the formula (I)    -   in which R¹, R² and R³, independently of one another, are        hydrogen, C₁-C₄-alkyl or phenyl, preferably        2-methyl-N-vinylimidazole or N-vinylimidazole    -   N,N-diallylamine of the formula (II),    -   in which R⁴ is a C₁-C₂₄-alkyl radical, preferably        N,N-diallyl-N-methylamine    -   N,N-diallylaminoalkyl derivatives of acrylic or methacrylic acid        of the formula (III)    -   in which R⁵ and R⁶, independently of one another, are hydrogen        or methyl, Z is a nitrogen atom where x=0, R⁷ is a linear or        branched C₁-C₂₄-alkylene radical, and R⁸ and R⁹, independently        of one another, are a C₁-C₂₄-alkylene radical.

Examples of compounds of the formula (I) are given in table 1 below:TABLE 1 R¹ R² R³ H H H Me H H H Me H H H Me Me Me H H Me Me Me H Me Ph HH H Ph H H H Ph Ph Me H Ph H Me Me Ph H H Ph Me H Me Ph Me H PhMe = methylPh = phenyl

Further monomers of the formula (I) which can be used are the ethyl,propyl or butyl analogs of the methyl-substituted 1-vinylimidazoleslisted in table 1.

Examples of compounds of the formula (II) are diallylamines, in which R⁴is methyl, ethyl, iso- or n-propyl, iso-, n- or tert-butyl, pentyl,hexyl, heptyl, octyl, nonyl or decyl. Examples of longer-chain radicalsR⁴ are undecyl, dodecyl, tridecyl, pentadecyl, octadecyl and icosyl.

Suitable monomers of the formula (III) are, for example,N,N-dimethylaminomethyl (meth)acrylate, N,N-diethylaminomethyl(meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate,N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminobutyl(meth)acrylate, N,N-diethylaminobutyl (meth)acrylate,N,N-dimethylaminohexyl (meth)acrylate, N,N-dimethylaminooctyl(meth)acrylate, N,N-dimethylaminododecyl (meth)acrylate,N-[3-(dimethylamino)propyl]acrylamide,N-[3-(dimethylamino)butyl]methacrylamide,N-[8-(dimethylamino)octyl]methacrylamide,N-[12-(dimethylamino)dodecyl]methacrylamide,N-[3-(diethylamino)propyl]methacrylamide orN-[3-(diethylamino)propyl]acrylamide, or mixtures thereof.

Preferred monomers (a) are 3-methyl-1-vinylimidazolium chloride andmethosulfate, dimethyldiallylammonium chloride, andN,N-dimethylaminoethyl methacrylate andN-[3-(dimethylamino)propyl]methacrylamide, which have optionally beenquaternized by methyl chloride, dimethyl sulfate or diethyl sulfate.

Particularly preferred monomers (a) are 3-methyl-1-vinylimidazoliumchloride and methosulfate and dimethyldiallylammonium chloride and veryparticular preference is given to 3-methyl-1-vinylimidazolium chlorideand methosulfate.

It is also possible to use mixtures of the monomers (a).

The monomers (a) are used for the application according to the inventionin amounts of from 1 to 99.9% by weight, preferably from 5 to 70% byweight and very particularly preferably from 10 to 50% by weight. The %by weight amount refers to the total amount of monomers (a) to (e) usedfor the preparation of the polymer.

The monomers (a) can be used either in quaternized form as monomers orbe polymerized in nonquaternized form, where, in the latter case, theresulting copolymer is either quaternized or protonated. In cases wherethe monomers are used in quaternized form, they can be used either asdried substance or in the form of concentrated solutions in solventssuitable for the monomers, for example in polar solvents, such as water,methanol, ethanol, acetone or electrolyte solutions.

Suitable for the protonation are, for example, mineral acids, such asHCl, H₂SO₄, and monocarboxylic acids, e.g. formic acid and acetic acid,dicarboxylic acids and polyfunctional carboxylic acids, e.g. oxalic acidand citric acid, and all other proton-releasing compounds and substanceswhich are able to protonate the corresponding nitrogen atom. Inparticular, water-soluble acids are suitable for the protonation.

The protonation of the polymer can either be carried out after thepolymerization or during the formulation of the cosmetic preparation,during which a physiologically compatible pH is usually set.

Protonation is understood as meaning that at least some of theprotonatable groups of the polymer, preferably 20 to 100%, isprotonated, resulting in an overall cationic charge of the polymer.

Suitable for the quaternization of the compounds of the formulae (I) to(III) are, for example, alkyl halides having 1 to 24 carbon atoms in thealkyl group, e.g. methyl chloride, methyl bromide, methyl iodide, ethylchloride, ethyl bromide, propyl chloride, hexyl chloride, dodecylchloride, lauryl chloride and benzyl halides, in particular benzylchloride and benzyl bromide. Further suitable quaternizing agents aredialkyl sulfates, in particular dimethyl sulfate or diethyl sulfate. Thequaternization of the basic monomers of the formulae (I) to (III) canalso be carried out with alkylene oxides, such as ethylene oxide orpropylene oxide, in the presence of acids.

The quaternization of the monomer or of a polymer with one of saidquaternization agents can take place by generally known methods.

Preferred quaternizing agents are: methyl chloride, dimethyl sulfate ordiethyl sulfate.

As monomers of group (b), preference is given to those compounds whichdissolve in water to an amount of more than 5% by weight at atemperature of 25° C. If they comprise polymeric monomers of group (b),then they may be present in amounts up to 98.98% by weight. Particularlypreferably, they are present in amounts of from 22 to 97.98% by weight,in particular from 45 to 85% by weight.

Suitable water-soluble monomers (b) different from (a) areN-vinyllactams, e.g. N-vinylpiperidone, N-vinylpyrrolidone andN-vinylcaprolactam, N-vinylacetamide, N-methyl-N-vinylacetamide,N-vinylformamide, acrylamide, methacrylamide, N,N-dimethylacrylamide,N-methylolmethacrylamide, N-vinyloxazolidone, N-vinyltriazole,hydroxyalkyl (meth)acrylates, e.g. hydroxyethyl (meth)acrylate andhydroxypropyl (meth)acrylates, or alkyl ethylene glycol (meth)acrylateswith 1 to 50 ethylene glycol units in the molecule.

Particular preference is given to using N-vinyllactams as monomers (b).Very particular preference is given to N-vinylpyrrolidone.

The monomers (b) are used for the application according to the inventionin amounts of from 0.1 to 99% by weight, preferably 10 to 95% by weightand very particularly preferably 40 to 90% by weight. The % by weightamount refers to the total amount of monomers a) to e) used for thepreparation of the polymer.

Suitable monomers (c) different from monomers (a) and (b) areC₁-C₄₀-alkyl esters of (meth)acrylic acid, where the esters are derivedfrom linear, branched-chain or carbocyclic alcohols, e.g. methyl(meth)acrylate, ethyl (meth)acrylate, tert-butyl (meth)acrylate,isobutyl (meth)acrylate, n-butyl (meth)acrylate, stearyl (meth)acrylate,or esters of alkoxylated fatty alcohols, e.g. C₁-C₄₀-fatty alcohols,reacted with ethylene oxide, propylene oxide or butylene oxide, inparticular C₁₀-C₁₈-fatty alcohols, reacted with 3 to 150 ethylene oxideunits. Also suitable are N-alkyl-substituted acrylamides with linear,branched-chain or carbocyclic alkyl radicals, such asN-tert-butylacrylamide, N-butylacrylamide, N-octylacrylamide,N-tert-octylacrylamide.

Also suitable are styrene, vinyl esters and allyl esters ofC₁-C₄₀-carboxylic acids, which may be linear, branched-chain orcarbocyclic, e.g. vinyl acetate, vinyl propionate, vinyl neononanoate,vinyl neoundecanoic acid, vinyl t-butylbenzoate, alkyl vinyl ethers, forexample methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether,stearyl vinyl ether.

Acrylamides, such as N-tert-butylacrylamide, N-butylacrylamide,N-octylacrylamide, N-tert-octylacrylamide and N-alkyl-substitutedacrylamides with linear, branched-chain or carbocyclic alkyl radicals,where the alkyl radical can have the meanings given above for R⁴.

Suitable monomers (c) are, in particular, C₁- to C₂₄-, very particularlyC₁- to C₁₀, alkyl esters of (meth)acrylic acid, e.g. methyl(meth)acrylate, ethyl (meth)acrylate, tert-butyl (meth)acrylate,isobutyl (meth)acrylate, n-butyl (meth)acrylate and acrylamides, such asN-tert-butylacrylamide or N-tert-octylacrylamide.

If they comprise polymeric monomers of group (c), they may be presenttherein in amounts of up to 50% by weight, in particular up to 40% byweight, preferably up to 30% by weight.

Suitable crosslinkers (monomers (e)) are, for example, acrylic esters,methacrylic esters, allyl ethers or vinyl ethers of at least dihydricalcohols. The OH groups of the parent alcohols may be completely orpartially etherified or esterified; however, the crosslinkers contain atleast two ethylenically unsaturated groups.

Examples of the parent alcohols are dihydric alcohols, such as1,2-ethanediol, 1,2-propanediol, 1,3-butanediol, 2,3-butanediol,1,4-butanediol, but-2-ene-1,4-diol, 1,2-pentanediol, 1,5-pentanediol,1,2-hexanediol, 1,5-hexanediol, 1,10-decanediol, 1,2-dodecanediol,1,12-dodecanediol, neopentyl glycol, 3-methylpentane-1,5-diol,2,5-dodecanediol, 1,12-dodecanediol, neopentyl glycol,3-methylpentane-1,5-diol, 2,5-dimethyl-1,3-hexanediol,2,2,4-trimethyl-1,3-pentanediol, 1,2-cyclohexanediol,1,4-cyclohexanediol, 1,4-bis(hydroxymethyl)cyclohexane, mononeopentylglycol hydroxypivalate, 2,2-bis(4-hydroxyphenyl)propane,2,2-bis[4-(2-hydroxypropyl)phenyl]propane, diethylene glycol,triethylene glycol, tetraethylene glycol, dipropylene glycol,tripropylene glycol, tetrapropylene glycol, 3-thiopentane-1,5-diol, andpolyethylene glycols, polypropylene glycols and polytetrahydrofuranswith molecular weights of in each case 200 to 10 000. As well as thehomopolymers of ethylene oxide or propylene oxide, it is also possibleto use block copolymers of ethylene oxide or propylene oxide orcopolymers which contain ethylene oxide and propylene oxide groups inincorporated form. Examples of parent alcohols with more than two OHgroups are trimethylolpropane, glycerol, pentaerythritol,1,2,5-pentanetriol, 1,2,6-hexanetriol, triethoxycyanuric acid, sorbitan,sugars, such as sucrose, glucose, mannose. It is of course also possibleto use the polyhydric alcohols following reaction with ethylene oxide orpropylene oxide as the corresponding ethoxylates or propoxylates,respectively. The polyhydric alcohols can also be firstly converted intothe corresponding glycidyl ethers by reaction with epichlorohydrin.

Further suitable crosslinkers are the vinyl esters or the esters ofmonohydric, unsaturated alcohols with ethylenically unsaturatedC₃-C₆-carboxylic acids, for example acrylic acid, methacrylic acid,itaconic acid, maleic acid or fumaric acid. Examples of such alcoholsare allyl alcohol, 1-buten-3-ol, 5-hexen-1-ol, 1-octen-3-ol,9-decen-1-ol, dicyclopentenyl alcohol, 10-undecen-1-ol, cinnamylalcohol, citronellol, crotyl alcohol or cis-9-octadecen-1-ol. It is,however, also possible to esterify the monohydric, unsaturated alcoholswith polybasic carboxylic acids, for example malonic acid, tartaricacid, trimellitic acid, phthalic acid, terephthalic acid, citric acid orsuccinic acid.

As crosslinkers, it is likewise possible to use esters of unsaturatedcarboxylic acids with the polyhydric alcohols described above, forexample maleic acid, crotonic acid, cinnamic acid or 10-undecenoic acid.

Also suitable are straight-chain or branched, linear or cyclic,aliphatic or aromatic hydrocarbons which have at least two double bonds,which in the case of aliphatic hydrocarbons must not be conjugated, e.g.divinylbenzene, divinyltoluene, 1,7-octadiene, 1,9-decadiene,4-vinyl-1-cyclohexene, trivinylcyclohexane or polybutadienes withmolecular weights of from 200 to 20 000.

Further suitable crosslinkers are the acrylamides, methacrylamides andN-allylamines of at least difunctional amines. Such amines are, forexample, 1,2-diaminomethane, 1,2-diaminoethane, 1,3-diaminopropane,1,4-diaminobutane, 1,6-diaminohexane, 1,12-dodecanediamine, piperazine,diethylenetriamine or isophoronediamine. Likewise suitable are theamides of allylamine and unsaturated carboxylic acids, such as acrylicacids, methacrylic acid, itaconic acid, maleic acid, or at least dibasiccarboxylic acids, as have been described above.

Further suitable as crosslinkers are triallylamine andtriallylmonoalkylammonium salts, e.g. triallylmethylammonium chloride ormethylsulfate.

Also suitable are N-vinyl compounds of urea derivatives, at leastdifunctional amides, cyanurates or urethanes, for example of urea,ethyleneurea, propyleneurea, or tartramide, e.g.N,N′-divinylethyleneurea or N,N′-divinylpropyleneurea.

Also suitable are alkylenebisacrylamides, such as methylenebisacrylamideand N,N′-(2,2-)butane and1,1′-bis(3,3′-vinylbenzimidazolith-2-one)-1,4-butane.

Other suitable crosslinkers are, for example, alkylene glycoldi(meth)acrylates, such as ethylene glycol diacrylate, ethylene glycoldimethacrylate, tetraethylene glycol acrylate, tetraethylene glycoldimethacrylate, diethylene glycol acrylate, diethylene glycolmethacrylate, vinyl acrylate, allyl acrylate, allyl methacrylate,divinyldioxane, pentaerythritol triallyl ether, and mixtures of thecrosslinkers.

Further suitable crosslinkers are divinyldioxane, tetraallylsilane ortetravinylsilane.

Crosslinkers which are used particularly preferably are, for example,methylenebisacrylamide, triallylamine and triallylalkylammonium salts,pentaerythritol triallyl ether, divinylimidazole,N,N′-divinylethyleneurea, reaction products of polyhydric alcohols withacrylic acid or methacrylic acid, methacrylic esters and acrylic estersof polyalkylene oxides or polyhydric alcohols which have been reactedwith ethylene oxide and/or propylene oxide and/or epichlorohydrin. Veryparticularly preferred crosslinkers are methylenebisacrylamide,N,N′-divinylethyleneurea and acrylic esters of glycol, butanediol,trimethylolpropane or glycerol or acrylic esters of glycol, butanediol,trimethylolpropane or glycerol reacted with ethylene oxide and/orepichlorohydrin.

Very particularly preferred crosslinkers are pentaerythritol triallylether, methylenebisacrylamide, N,N′-divinylethyleneurea, triallylamineand triallylmonoalkylammonium salts, and acrylic esters of glycol,butanediol, trimethylolpropane or glycerol or acrylic esters of glycol,butanediol, trimethylolpropane or glycerol reacted with ethylene oxideand/or epichlorohydrin.

It is of course also possible to use mixtures of the abovementionedcompounds. The crosslinker is preferably soluble in the reaction medium.If the solubility of the crosslinker in the reaction medium is low, itmay be dissolved in a monomer or in a monomer mixture, or else bemetered in in dissolved form in a solvent which is miscible with thereaction medium. Particular preference is given to those crosslinkerswhich are soluble in the monomer mixture.

The solution viscosity of the polymers according to the invention can beinfluenced to a wide degree by means of the content of crosslinkers.

The crosslinkers e) are used for the application according to theinvention in amounts of from 0.05 to 10% by weight, preferably 0.07 to5% by weight and very particularly preferably 0.1 to 2.5% by weight. The% by weight amount refers to the total amount of monomers a) to e) usedfor the preparation of the polymer.

The salt is used in order to deposit the polymer as it rises in aseparate phase and thus to reduce the overall viscosity of the aqueousdispersion. The polymerization of the water-soluble monomers givesparticles of water-soluble polymer if thorough mixing is adequatelyprovided for.

The choice of the corresponding salts depends on the polymer to begenerated and the protective colloid used. The choice of type and amountof salt should be such that the polymer to be prepared is insoluble inthe salt solution.

The salts to be used which can be used for the precipitation of thepolymer are described in detail in WO 98/14405 and WO 00/20470, whichare hereby expressly incorporated by reference.

Particularly suitable salts are inorganic salts, preferably cosmotropicones, such as chlorides, sulfates, phosphates or hydrogenphosphates ofmetal ions or ammonium ions. Typical representatives are sodium sulfate,potassium sulfate, ammonium sulfate, magnesium sulfate, aluminumsulfate, sodium chloride, calcium chloride, sodium dihydrogenphosphate,diammonium hydrogenphosphate, dipotassium hydrogenphosphate, calciumphosphate, sodium citrate and iron sulfate.

These salts can be used individually or as mixtures of two or moresalts. Often a mixture of two or more salts is more effective than onesalt on its own, based on the amount used.

Chaotropic salts, such as thiocyanates, perchlorates, chlorates,nitrates, bromides and iodides, can likewise be used. Typicalrepresentatives are calcium nitrate, sodium nitrate, ammonium nitrate,aluminum nitrate, sodium thiocyanate and sodium iodide.

The salts are added in an amount which is 1 to 100%, preferably 10 to90% and particularly preferably 25 to 75%, of the saturation amount inthe reaction medium.

100% saturation amount in the reaction medium is understood as meaningthat amount of salt or salts which just still dissolve in the aqueoussolution of the monomers used at the reaction temperature used withoutprecipitation.

The polymeric water-soluble protective colloids in the water-in-wateremulsions according to the invention are generally dissolved in theaqueous phase, although small amounts may be found in the dispersedphase. The amount of protective colloid in the continuous and dispersedphase can be determined using known analytical methods, such as Ramanmicroscopy. In the absence of the protective colloid, no low-viscositydispersion is formed, but a highly viscous gel is obtained.

The polymeric protective colloids contain at least one functional groupchosen from ether, hydroxyl, carboxyl, sulfone, sulfate ester, ester,amino, amido, imino, tert-amino and/or quaternary ammonium groups.Examples of the protective colloids which may be mentioned are:cellulose derivatives, polyethylene glycol, polypropylene glycol,copolymers of ethylene glycol and propylene glycol, polyvinyl acetates,polyvinyl alcohol, starch and starch derivatives, guar gum and guar gumderivatives, dextran, polyvinyl 2-methylsuccinimide, polyvinyl1,3-oxazolidone-2, polyvinyl-2-methylimidazoline, and copolymers which,as well as combinations of monomeric building blocks of theabovementioned polymers can contain, for example, the following monomerunits: maleic acid, maleic anhydride, fumaric acid, itaconic acid,itaconic anhydride, (meth)acrylic acid, salts of (meth)acrylic acid or(meth)acrylamide compounds.

As neutral protective colloids, preference is given to usingpolyalkylene ethers, such as, for example, polyethylene glycol,polypropylene glycol or polybutylene 1,4-ether and starch and starchderivatives. The preparation of polyalkylene ethers is known, forexample, from Kirk-Othmer, Encyclopedia of Chemical Technology, 3^(rd)Ed., Vol. 18, pp. 616-670, 1982, Wiley Interscience. Particularlypreferred neutral protective colloids are polyalkylene ethers, such as,for example, polyethylene glycol, polypropylene glycol or polybutylene1,4-ether.

Preferred protective colloids are homopolymers or copolymers of thefollowing monomers:

a) Anionic Monomers:

-   -   acrylic acid, methacrylic acid, ethacrylic acid, maleic acid,        itaconic acid, 2-acrylamido-2-methylpropanesulfonic acid,        vinylsulfonic acid, vinylsulfuric acid, vinylphosphoric acid,        styrenesulfonic acid, styrenesulfuric acid and ammonium and        alkali metal salts thereof. Anionic radicals can also be formed        after the reaction by hydrolysis of (meth)acrylamide or        (meth)acrylate units.        b) Cationic Monomers:    -   Preference is given to using vinylimidazoles, dialkylaminoalkyl        (alk)acrylates, dialkylaminoalkylacrylamides,        diallylalkylammonium and vinylamine quaternized with dimethyl        sulfate, diethyl sulfate, or MeCl. The cationic charge can also        be produced by after-treatment of the polymer, for example by        quaternization (with methyl chloride or dimethyl sulfate,        diethyl sulfate) or by protonation of the monomers or by        hydrolysis, for example of vinylformamide to give vinylamine.        c) Neutral Water-Soluble Monomers:    -   N-Vinylpyridines, N-vinylacetamide, N-vinylpyrrolidone,        hydroxyalkyl (meth)acrylates, acrylamide, methacrylamide, VFA,        PEG-acrylates and methacrylate derivatives, acrylates and        acrylamides with an additional nitrogen function, such as        DMAEMA, N-vinylcaprolactam.        d) Neutral Hydrophobic Monomers:    -   Acrylates and styrenes with low solubility in water in as far as        these sparingly water-soluble units do not render the resulting        polymer overall water-insoluble or water-unswellable. Examples        which may be mentioned are: butadiene, α-alkenes,        vinylcyclohexane, vinyl halides, acrylonitrile, alkyl        (alk′)acrylates or aryl (alk)acrylates in which the alkyl or        aryl group has about 1 to 12 carbon atoms, such as methyl        (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate,        butyl (meth)acrylate, hexyl (meth)acrylate, ethylhexyl        (meth)acrylate, isoalkyl (meth)acrylate, cyclohexyl        (meth)acrylate or aromatic (meth)acrylates or alkyl or        aryl(alk)acrylamides in which the alkyl or aryl group carries        about 1 to 12 carbon atoms, such as methylmeth(acrylamide),        ethylmeth(acrylamide), ethylmeth(acrylamide),        t-butylmeth(acrylamide), dimethylmeth(acrylamide),        hexylmeth(acrylamide), ethylhexylmeth(acrylamide),        isoalkylmeth(acrylamide), cyclohexylmeth(acrylamide), or        aromatic meth(acrylamides), t-butylacrylamide.

As protective colloids, particular preference is given to using neutralwater-soluble polymers, for example polyvinyl alcohol,polyvinylformamide, polyvinylpyrrolidone, poly(meth)acrylamide,polyhydroxyalkyl (meth)acrylate, and homopolymers and copolymers of themonomers under c) and d).

As protective colloids, particular preference is given to usingpolyelectrolytes, such as, for example, polymers, comprising monomerbuilding blocks, such as, for example, salts of (meth)acrylic acid asanionic monomer building blocks or methyl chloride-quaternizedderivatives of N,N-dimethylaminoethyl (meth)acrylate,N,N-dimethylaminopropyl (meth)acrylate or N,N-dimethylaminohydroxypropyl(meth)acrylate or N,N-dimethylaminopropyl(meth)acrylamide, andhomopolymers and copolymers of the monomers under a) and b), copolymersof the monomers a) and c), a) and d), b) and c), b) and d).

The overall charge of the polyelectrolyte can either be positive ornegative. The polyelectrolyte should be water-soluble even if it isbuilt up from monomers which are not particularly readily water-soluble.

The K values of the protective colloids are in a range between 10 and350, preferably 20 to 200 and particularly preferably 35 to 110. The Kvalues are measured in accordance with Fikentscher, Cellulosechemie,Vol. 13, pp. 58-64 (1932) at 25° C. as 0.1% strength in 5% by weightsodium chloride solution.

These protective colloids can be used individually or as mixtures of twoor more protective colloids.

The protective colloids are used in amounts of from 0.1 to 30% byweight, preferably 0.5 to 20% by weight and particularly preferably 1 to10% by weight, based on the total weight of the dispersion.

Total weight of the dispersion is understood as meaning the weight ofthe monomers used, of the water used and of the salts used.

Initiators which can be used for the free-radical polymerization are thewater-soluble and water-insoluble peroxo and/or azo compounds, forexample alkali metal or ammonium peroxydisulfates, hydrogen peroxide,dibenzoyl peroxide, tert-butyl perpivalate,2,2′-azobis(2,4-dimethylvaleronitrile), tert-butyl peroxineodecanoate,tert-butyl per-2-ethylhexanoate, di-tert-butyl peroxide, tert-butylhydroperoxide, azobisisobutyronitrile,azobis(2-amidinopropane)dihydrochloride or2,2′-azobis(2-methylbutyronitrile). Also suitable are initiator mixturesor redox initiator systems, such as, for example, ascorbic acid/iron(II)sulfate/sodium peroxodisulfate, tert-butyl hydroperoxide/sodiumdisulfite, tert-butyl hydroperoxide/sodium hydroxymethanesulfinate. Theinitiators can be used in the customary amounts, for example 0.05 to 7%by weight, based on the amount of the monomers to be polymerized.

The co-use of redox coinitiators, for example benzoin, dimethylanilineand organically soluble complexes and salts of heavy metals, such ascopper, cobalt, manganese, nickel and chromium or, in particular, iron,can reduce the half-life times of said peroxides, particularly of thehydroperoxides, meaning that, for example, tert-butyl hydroperoxide iseffective in the presence of 5 ppm of copperII acetylacetonate even at100° C.

Preference is given to using readily water-soluble initiators.

The polymerization reaction is started with the help of polymerizationinitiators which decompose into free radicals. It is possible to use allinitiators which are known for the polymerization of the monomers. Forexample, initiators which decompose into free radicals and which havehalf-life times of less than three hours at the temperature chosen inthe particular case are suitable. If the polymerization is carried outat different temperatures by carrying out initial polymerization of themonomers firstly at a lower temperature and then completing thepolymerization at a significantly higher temperature, then use isexpediently made of at least two different initiators which have anadequate rate of decomposition in the temperature range chosen in theparticular case.

The polymerization is usually carried out at temperatures between 20 and100° C., preferably between 30 and 90° C., 40 and 80° C., and atatmospheric pressure or under autogenous pressure.

The polymerization can optionally also be carried out in the presence ofpolymerization regulators in order to regulate the molecular weight ofthe polymers. If the aim is to prepare particularly low molecular weightcopolymers, larger amounts of polymerization regulators are used,whereas for the preparation of high molecular weight copolymers onlysmall amounts of polymerization regulators are used or thepolymerization is carried out in the absence of these substances.Suitable polymerization regulators are, for example, 2-mercaptoethanols,mercaptopropanols, mercaptobutanols, thioglycolic acid,N-dodecylmercaptan, tert-dodecylmercaptan, thiophenol, mercaptopropionicacid, allyl alcohol and acetaldehyde. The polymerization regulators areused, based on the monomers used, in an amount of from 0 to 10% byweight, preferably 0 to 5% by weight, particularly preferably 0 to 2% byweight.

Customary processing auxiliaries, such as complexing agents, buffers,odorants, can be added where necessary. Viscosity modifiers, such asglycerol, methanol, ethanol, t-butanol, glycol, etc., can likewise beadded to the aqueous dispersion.

The polymerization is carried out in a preferred embodiment as a batchprocedure. In this connection, it is preferred to initially introducethe monomers (a-c) into the vessel.

In a preferred embodiment, the processes according to the invention arecarried out as feed processes. Here, individual reactants or all of thereactants are added, completely or partially, in portions orcontinuously, together or in separate feeds, to a reaction mixture. Itis, however, also possible to meter in the initiator to the initialcharge heated to the polymerization temperature and comprising thesalts, protective colloids, and monomers (a) to (e). In a furthervariant the initiator and the crosslinker (d) are added to a mixture ofmonomers (a) and optionally monomers (b) and (c) after thepolymerization temperature has been reached. It is also possible to heatthe initial charge comprising the salt and protective colloids to thepolymerization temperature and to add initiator and monomers (d) inseparate feeds or together. It is of course also possible to addinitiator, monomers (d) and monomers (a) and optionally monomers (b) and(c) to an initial charge heated to the polymerization temperature andcomprising a mixture of salts and protective colloids. Preference isgiven to using a mixture of salt and protective colloid in water or amixture of salt or protective colloid in water and at least part of themonomers (a) and optionally (b) and (c), and optionally furthercomponents as the initial charge.

The dispersions are usually milky white and have a viscosity of from 100to 50 000 mPas, preferably from 200 to 20 000 mPas, particularlypreferably from 300 to 15 000 mPas.

The dispersions produced in the polymerization can, after thepolymerization process, be subjected to a physical or chemicalafter-treatment. Such processes are, for example, the known processesfor reducing residual monomers, such as, for example, after-treatment byadding polymerization initiators or mixtures of two or morepolymerization initiators at suitable temperatures or heating thepolymerization solution to temperatures above the polymerizationtemperature, an after-treatment of the polymer solution by means ofsteam or stripping with nitrogen or treatment of the reaction mixturewith oxidizing or reducing reagents, adsorption processes, such as theadsorption of contamination on selected media, such as, for example,activated carbon, or an ultrafiltration. It can also be followed by theknown work-up steps, for example suitable drying processes, such asspray-drying, freeze-drying or roll-drying, or agglomeration processesfollowing the drying. The dispersions with a low content of residualmonomers obtained by the process according to the invention can also besold directly.

The polymers according to the invention can advantageously be used incosmetic preparations, in particular hair cosmetic preparations.

The term “cosmetic preparations” is to be understood in the broad senseand means all those preparations which are suitable for application toskin and/or hair and/or nails and pursue a purpose other than a purelymedicinal-therapeutic purpose.

The polymers according to the invention can be used in skin cosmeticpreparations.

For example, the polymers according to the invention are used incosmetic compositions for cleansing the skin. Such cosmetic cleansingcompositions are chosen from bar soaps, such as toilet soaps, curdsoaps, transparent soaps, luxury soaps, deodorizing soaps, cream soaps,baby soaps, skin protection soaps, abrasive soaps and syndets, liquidsoaps, such as pasty soaps, soft soaps and washing paste, and liquidwashing, shower and bath preparations, such as washing lotions, showerbaths and shower gels, foam baths, oil baths and scrub preparations.

Preferably, the polymers according to the invention are used in cosmeticcompositions for the care and protection of the skin, in nailcarecompositions and in preparations for decorative cosmetics.

Particular preference is given to the use in skincare compositions,intimate care compositions, footcare compositions, deodorants, lightprotection compositions, repellants, shaving compositions, hair-removalcompositions, anti-acne compositions, make-up, mascara, lipsticks,eyeshadows, kohl pencils, eyeliners, blushers, powders and eyebrowpencils.

The skincare compositions are in particular in the form of W/O or O/Wskin creams, day and night creams, eye creams, face creams, antiwrinklecreams, moisturizing creams, bleaching creams, vitamin creams, skinlotions, care lotions and moisturizing lotions.

The polymers according to the invention can develop particular effectsin the cosmetic preparations. The polymers can, inter alia, contributeto the moisturization and conditioning of the skin and to theimprovement in the feel of the skin. The polymers can also act asthickeners in the formulations. The addition of the polymers accordingto the invention can, in certain formulations, bring about aconsiderable improvement in the skin compatibility.

The copolymers according to the invention are present in the skincosmetic preparations in an amount of from about 0.001 to 20% by weight,preferably 0.01 to 10% by weight, very particularly preferably 0.1 to 5%by weight, based on the total weight of the composition.

Depending on the field of use, the compositions according to theinvention can be applied in a form suitable for skincare, such as, forexample, in the form of a cream, foam, gel, stick, powder, mousse, milkor lotion.

As well as the polymers according to the invention and suitablesolvents, the skin cosmetic preparations can also comprise additivescustomary in cosmetics, such as emulsifiers, preservatives, perfumeoils, cosmetic active ingredients, such as phytantriol, vitamin A, E andC, retinol, bisabolol, panthenol, light protection agents, bleachingagents, colorants, tinting agents, tanning agents (e.g.dihydroxyacetone), collagen, protein hydrolysates, stabilizers, pHregulators, dyes, salts, thickeners, gel formers, bodying agents,silicones, humectants, refatting agents and further customary additives.

Suitable solvents which may be mentioned are, in particular, water andlower monoalcohols or polyols having 1 to 6 carbon atoms or mixturesthereof; preferred monoalcohols or polyols are ethanol, isopropanol,propylene glycol, glycerol and sorbitol.

As further customary additives, fatty bodies may be present, such asmineral and synthetic oils, such as, for example, paraffins, siliconeoils and aliphatic hydrocarbons having more than 8 carbon atoms, animaland vegetable oils, such as, for example, sunflower oil, coconut oil,avocado oil, olive oil, lanolin, or waxes, fatty acids, fatty acidesters, such as, for example, triglycerides of C₆-C₃₀-fatty acids, waxesters, such as, for example, jojoba oil, fatty alcohols, vaseline,hydrogenated lanolin and acetylated lanolin. It is of course alsopossible to use mixtures thereof.

Customary thickeners in such formulations are crosslinked polyacrylicacids and derivatives thereof, polysaccharides, such as xanthan gum,agar agar, alginates or tyloses, carboxymethylcellulose orhydroxycarboxymethylcellulose, fatty alcohols, monoglycerides and fattyacids, polyvinyl alcohol and polyvinylpyrrolidone.

The polymers according to the invention can also be mixed with customarypolymers if specific properties are to be set.

Examples of suitable conventional polymers are anionic, cationic,amphoteric and neutral polymers.

Examples of anionic polymers are homopolymers and copolymers of acrylicacid and methacrylic acid or salts thereof, copolymers of acrylic acidand acrylamide and salts thereof; sodium salts of polyhydroxycarboxylicacids, water-soluble or water-dispersible polyesters, polyurethanes andpolyureas. Particularly suitable polymers are copolymers of t-butylacrylate, ethyl acrylate, methacrylic acid (e.g. Luvimer® 100P),copolymers of ethyl acrylate and methacrylic acid (e.g. Luvimer® MAE),copolymers of N-tert-butylacrylamide, ethyl acrylate, acrylic acid(Ultrahold® 8, strong), copolymers of vinyl acetate, crotonic acid andoptionally further vinyl esters (e.g. Luviset® grades), maleic anhydridecopolymers, optionally reacted with alcohols, anionic polysiloxanes,e.g. carboxyfunctional, copolymers of vinylpyrrolidone, t-butylacrylate, methacrylic acid (e.g Luviskol® VBM), copolymers of acrylicacid and methacrylic acid with hydrophobic monomers, such as, forexample, C₄-C₃₀-alkyl esters of meth(acrylic acid), C₄-C₃₀-alkylvinylesters, C₄-C₃₀-alkylvinyl ethers and hyaluronic acid.

Further suitable polymers are cationic polymers with the INCI namePolyquaternium, e.g. copolymers of vinylpyrrolidone/N-vinylimidazoliumsalts (Luviquat® FC, Luviquat® HM, Luviquat® MS, Luviquat® Care),copolymers of N-vinylpyrrolidone/dimethylaminoethyl methacrylate,quaternized with diethyl sulfate (Luviquat® PQ 11), copolymers ofN-vinylcaprolactam/N-vinylpyrrolidone/N-vinylimidazolium salts(Luviquat® Hold); cationic cellulose derivatives (Polyquaternium-4 and-10), acrylamide copolymers (Polyquaternium-7) and chitosan.

Suitable further polymers are also neutral polymers, such aspolyvinylpyrrolidones, copolymers of N-vinylpyrrolidone and vinylacetate and/or vinyl propionate, polysiloxanes, polyvinylcaprolactam andcopolymers containing N-vinylpyrrolidone, polyethylenimines and saltsthereof, polyvinylamines and salts thereof, cellulose derivatives,polyaspartic acid salts and derivatives.

To set certain properties, the preparations can additionally alsocomprise conditioning substances based on silicone compounds. Suitablesilicone compounds are, for example, polyalkylsiloxanes,polyarylsiloxanes, polyarylalkylsiloxanes, polyethersiloxanes orsilicone resins.

The copolymers according to the invention are used in cosmeticpreparations which are produced in accordance with the customaryguidelines known to the person skilled in the art.

Such formulations are advantageously in the form of emulsions,preferably in the form of water-in-oil (W/O) or oil-in-water (O/W)emulsions. It is, however, also possible and in some cases advantageousaccording to the invention to choose other types of formulation, forexample hydrodispersions, gels, oils, oleogels, multiple emulsions, forexample in the form of W/O/W or O/W/O emulsions, anhydrous ointments orointment bases etc.

The emulsions which can be used according to the invention are preparedby known methods.

As well as the copolymer according to the invention, the emulsionscomprise customary constituents, such as fatty alcohols, fatty acidesters and, in particular, fatty acid triglycerides, fatty acids,lanolin and derivatives thereof, natural or synthetic oils or waxes andemulsifiers in the presence of water.

The selection of additives specific to the type of emulsion and thepreparation of suitable emulsions is described, for example, inSchrader, Grundlagen und Rezepturen der Kosmetika [Fundamentals andFormulations of Cosmetics], Hüthig Buch Verlag, Heidelberg, 2nd edition,1989, third part, to which express reference is hereby made.

Thus, a skin cream which can be used according to the invention can bein the form, for example, of a W/O emulsion. An emulsion of this typecomprises an aqueous phase which is emulsified in an oil or fatty phaseby means of a suitable emulsifier system.

The concentration of the emulsifier system in this type of emulsion isabout 4 to 35% by weight, based on the total weight of the emulsion; thefatty phase constitutes about 20 to 60% by weight and the aqueous phaseabout 20 to 70% by weight, in each case based on the total weight of theemulsion. The emulsifiers are those which are customarily used in thistype of emulsion. They are chosen, for example, from: C₁₂-C₁₈-sorbitanfatty acid esters; esters of hydroxystearic acid and C₁₂-C₃₀-fattyalcohols; mono- and diesters of C₁₂-C₁₈-fatty acids and glycerol orpolyglycerol; condensates of ethylene oxide and propylene glycols;oxypropylenated/oxyethylenated C₁₂-C₂₀-fatty alcohols; polycyclicalcohols, such as sterols; aliphatic alcohols with a high molecularweight, such as lanolin; mixtures of oxypropylenated/polyglycerolatedalcohols and magnesium isostearate; succinic esters ofpolyoxyethylenated or polyoxypropylenated fatty alcohols; and mixturesof magnesium, calcium, lithium, zinc or aluminum lanolate andhydrogenated lanolin or lanolin alcohol.

Suitable fatty components which may be present in the fatty phase of theemulsions include hydrocarbon oils, such as paraffin oil, purcellin oil,perhydrosqualene and solutions of microcrystalline waxes in these oils;animal or vegetable oils, such as sweet almond oil, avocado oil,calophylum oil, lanolin and derivatives thereof, castor oil, sesame oil,olive oil, jojoba oil, karite oil, hoplostethus oil; mineral oils whosedistillation start point under atmospheric pressure is at about 250° C.and whose distillation end point is at 410° C., such as, for example,vaseline oil; esters of saturated or unsaturated fatty acids, such asalkyl myristates, e.g. isopropyl, butyl or cetyl myristate, hexadecylstearate, ethyl or isopropyl palmitate, octanoic or decanoic acidtriglycerides and cetyl ricinoleate.

The fatty phase may also comprise silicone oils soluble in other oils,such as dimethylpolysiloxane, methylphenylpolysiloxane and the siliconeglycol copolymer, fatty acids and fatty alcohols.

In order to favor the retention of oils, it is also possible to usewaxes, such as, for example, carnauba wax, candellila wax, beeswax,microcrystalline wax, ozokerite wax and Ca, Mg and Al oleates,myristates, linoleates and stearates.

In general, these water-in-oil emulsions are prepared by adding thefatty phase and the emulsifier to the batch container. The latter isheated at a temperature of from 70 to 75° C., then the oil-solubleingredients are added, and water which has been heated beforehand to thesame temperature and in which the water-soluble ingredients have beendissolved beforehand is added with stirring; the mixture is stirreduntil an emulsion of the desired fineness is achieved, which is thenleft to cool to room temperature, if necessary with a lesser amount ofstirring.

In addition, a care emulsion according to the invention may be in theform of a O/W emulsion. Such an emulsion usually comprises an oil phase,emulsifiers which stabilize the oil phase in the water phase, and anaqueous phase which is usually present in thickened form.

The aqueous phase of the O/W emulsion of the preparations according tothe invention optionally comprises

-   -   alcohols, diols or polyols and ethers thereof, preferably        ethanol, isopropanol, propylene glycol, glycerol, ethylene        glycol monoethyl ether;    -   customary thickeners or gel formers, such as, for example,        crosslinked polyacrylic acids and derivatives thereof,        polysaccharides, such as xanthan gum or alginates,        carboxymethylcellulose or hydroxycarboxymethylcellulose, fatty        alcohols, polyvinyl alcohol and polyvinylpyrrolidone.

The oil phase comprises oil components customary in cosmetics, such as,for example:

-   -   esters of saturated and/or unsaturated, branched and/or        unbranched C₃-C₃₀-alkanecarboxylic acids and saturated and/or        unsaturated, branched and/or unbranched C₃-C₃₀-alcohols, of        aromatic carboxylic acids and saturated and/or unsaturated,        branched and/or unbranched C₃-C₃₀-alcohols, for example        isopropyl myristate, isopropyl stearate, hexyldecyl stearate,        oleyl oleate; and also synthetic, semisynthetic and natural        mixtures of such esters, such as jojoba oil;    -   branched and/or unbranched hydrocarbons and hydrocarbon waxes;    -   silicone oils, such as cyclomethicone, dimethylpolysiloxane,        diethylpolysiloxane, octamethylcyclotetrasiloxane and mixtures        thereof;    -   dialkyl ethers;    -   mineral oils and mineral waxes;    -   triglycerides of saturated and/or unsaturated, branched and/or        unbranched C₈-C₂₄-alkanecarboxylic acids; they can be chosen        from synthetic, semisynthetic or natural oils, such as olive        oil, palm oil, almond oil or mixtures.

Suitable emulsifiers are, preferably O/W emulsifiers, such aspolyglycerol esters, sorbitan esters or partially esterified glycerides.

The preparation may be carried out by melting the oil phase at about 80°C.; the water-soluble constituents are dissolved in hot water, added tothe oil phase slowly and with stirring; homogenized and stirred untilcold.

The polymers according to the invention are also suitable for use inwashing and shower gel formulations and bath preparations.

As well as the polymers according to the invention, such formulationsusually comprise anionic surfactants as base surfactants and amphotericand nonionic surfactants as cosurfactants, and also lipids, perfumeoils, dyes, organic acids, preservatives and antioxidants, andthickeners/gel formers, skin conditioning agents and humectants.

In the washing, showering and bathing preparations, all anionic,neutral, amphoteric or cationic surfactants customarily used inbody-cleansing compositions may be used.

The formulations comprise 2 to 50% by weight of surfactants, preferably5 to 40% by weight, particularly preferably 8 to 30% by weight.

Suitable anionic surfactants are, for example, alkyl sulfates, alkylether sulfates, alkylsulfonates, alkylarylsulfonates, alkyl succinates,alkyl sulfosuccinates, N-alkoylsarcosinates, acyl taurates, acylisethionates, alkyl phosphates, alkyl ether phosphates, alkyl ethercarboxylates, alpha-olefinsulfonates, in particular the alkali metal andalkaline earth metal salts, e.g. sodium, potassium, magnesium, calcium,and ammonium and triethanolamine salts. The alkyl ether sulfates, alkylether phosphates and alkyl ether carboxylates can have between 1 and 10ethylene oxide or propylene oxide units, preferably 1 to 3 ethyleneoxide units, in the molecule.

Suitable compounds are, for example, sodium lauryl sulfate, ammoniumlauryl sulfate, sodium lauryl ether sulfate, ammonium lauryl ethersulfate, sodium lauryl sarcosinate, sodium oleyl succinate, ammoniumlauryl sulfosuccinate, sodium dodecylbenzenesulfonate, triethanolaminedodecylbenzenesulfonate.

Suitable amphoteric surfactants are, for example, alkylbetaines,alkylamidopropylbetaines, alkylsulfobetaines, alkyl glycinates, alkylcarboxyglycinates, alkyl amphoacetates or amphopropionates, alkylamphodiacetates or amphodipropionates.

For example, it is possible to use cocodimethylsulfopropylbetaine,laurylbetaine, cocamidopropylbetaine or sodium cocamphopropionate.

Suitable nonionic surfactants are, for example, the reaction products ofaliphatic alcohols or alkylphenols, having 6 to 20 carbon atoms in thealkyl chain, which may be linear or branched, with ethylene oxide and/orpropylene oxide. The amount of alkylene oxide is about 6 to 60 mol permole of alcohol. Also suitable are alkylamine oxides, mono- ordialkylalkanolamides, fatty acid esters of polyethylene glycols,ethoxylated fatty acid amides, alkyl polyglycosides or sorbitan etheresters.

In addition, the washing, shower and bathing preparations can comprisecustomary cationic surfactants, such as, for example, quaternaryammonium compounds, for example cetyltrimethylammonium chloride.

Additionally, further customary cationic polymers may also be used, suchas, for example, copolymers of acrylamide and dimethyldiallylammoniumchloride (Polyquaternium-7), cationic cellulose derivatives(Polyquaternium-4, -10), guar hydroxypropyltrimethylammonium chloride(INCI: Hydroxypropyl Guar Hydroxypropyltrimonium Chloride), copolymersof N-vinylpyrrolidone and quaternized N-vinylimidazole(Polyquaternium-16, -44, -46), copolymers ofN-vinylpyrrolidone/dimethylaminoethyl methacrylate, quaternized withdiethyl sulfate (Polyquaternium-11), and others.

In addition, the washing and shower gel formulations and bathingpreparations can comprise thickeners, such as, for example, sodiumchloride, PEG-55, propylene glycol oleate, PEG-120 methyl glucosedioleate and others, and also preservatives, further active ingredientsand auxiliaries and water.

Hair cosmetic preparations include, in particular styling compositionsand/or conditioning agents in hair cosmetic preparations, such as hairtreatments, hair mousses, hair gels or hair sprays, hair lotions, hairrinses, hair shampoos, hair emulsions, hair-end fluids, neutralizers forpermanent waves, hair colorants and bleaches, hot-oil treatmentpreparations, conditioners, setting lotions or hair sprays. Depending onthe field of application, the hair cosmetic preparations can be appliedin the form of (aerosol) spray, (aerosol) mousse, gel, gel spray, cream,lotion or wax.

In a preferred embodiment, the hair cosmetic formulations according tothe invention comprise

-   a) 0.05 to 20% by weight of the polymer according to the invention-   b) 20 to 99.95% by weight of water and/or alcohol-   c) 0 to 79.5% by weight of further constituents

Alcohol is understood as meaning all alcohols customary in cosmetics,e.g. ethanol, isopropanol, n-propanol.

Further constituents are understood as meaning the additives customaryin cosmetics, for example propellants, antifoams, interface-activecompounds, i.e. surfactants, emulsifiers, foam formers and solubilizers.The interface-active compounds used may be anionic, cationic, amphotericor neutral. Further customary constituents may also be, for example,preservatives, perfume oils, opacifiers, active ingredients, UV filters,care substances, such as panthenol, collagen, vitamins, proteinhydrolysates, alpha- and beta-hydroxycarboxylic acids, stabilizers, pHregulators, dyes, viscosity regulators, gel formers, salts, humectants,refatting agents, complexing agents and further customary additives.

Also included here are all styling and conditioning polymers known incosmetics which can be used in combination with the polymers accordingto the invention if very specific properties are to be set.

Examples of suitable conventional hair cosmetic polymers are anionicpolymers. Such anionic polymers are homopolymers and copolymers ofacrylic acid and methacrylic acid or salts thereof, copolymers ofacrylic acid and acrylamide and salts thereof; sodium salts ofpolyhydroxycarboxylic acids, water-soluble or water-dispersiblepolyesters, polyurethanes (Luviset® P.U.R.) and polyureas. Particularlysuitable polymers are copolymers of t-butyl acrylate, ethyl acrylate,methacrylic acid (e.g. Luvimer® 100P), copolymers ofN-tert-butylacrylamide, ethyl acrylate, acrylic acid (Ultrahold® 8,strong), copolymers of vinyl acetate, crotonic acid and optionallyfurther vinyl esters (e.g. Luviset® grades), maleic anhydridecopolymers, optionally reacted with alcohols, anionic polysiloxanes,e.g. carboxyfunctional ones, copolymers of vinylpyrrolidone, t-butylacrylate, methacrylic acid (e.g. Luviskol® VBM).

In addition, the group of polymers suitable for the combination with thepolymers according to the invention includes, by way of example,Balance® CR (National Starch; acrylate copolymer), Balance® 0/55(National Starch; acrylate copolymer), Balance® 47 (National Starch;octylacrylamide/acrylate/butylaminoethyl methacrylate copolymer),Aquaflex® FX 64 (ISP; isobutylene/ethylmaleimide/hydroxyethylmaleimidecopolymer), Aquaflex® SF-40 (ISP/National Starch; VP/vinylcaprolactam/DMAPA acrylate copolymer), Allianz® LT-120 (ISP/Rohm & Haas;acrylate/C1-2 succinate/hydroxyacrylate copolymer), Aquarez® HS(Eastman; polyester-1), Diaformer® Z-400 (Clariant;methacryloylethylbetaine/methacrylate copolymer), Diaformer® Z-711(Clariant; methacryloylethyl N-oxide/methacrylate copolymer), Diaformer®Z-712 (Clariant; methacryloylethyl N-oxide/methacrylate copolymer),Omnirez® 2000 (ISP; monoethyl ester of poly(methyl vinyl ether/maleicacid) in ethanol), Amphomer® HC (National Starch;acrylate/octylacrylamide copolymer), Amphomer® 28-4910 (National Starch;octylacrylamide/acrylate/butylaminoethyl methacrylate copolymer),Advantage® HC 37 (ISP; terpolymer ofvinylcaprolactam/vinylpyrrolidone/dimethylaminoethyl methacrylate),Acudyne® 258 (Rohm & Haas; acrylate/hydroxy ester acrylate copolymer),Luviset® PUR (BASF, polyurethane-1), Luviflex® Silk (BASF), Eastman®AQ48 (Eastman).

Very particularly preferred anionic polymers are acrylates with an acidnumber greater than or equal to 120 and copolymers of t-butyl acrylate,ethyl acrylate, methacrylic acid.

Further suitable hair cosmetic polymers are cationic polymers with theINCI name polyquaternium, e.g. copolymers ofvinylpyrrolidone/N-vinylimidazolium salts (Luviquat® FC, Luviquat® HM,Luviquat® MS, Luviquat® Care, copolymers ofN-vinylpyrrolidone/dimethylaminoethyl methacrylate, quaternized withdiethyl sulfate (Luviquat® PQ 11), copolymers of N-vinylcaprolactamN-vinylpyrrolidone/N-vinylimidazolium salts (Luviquat® Hold); cationiccellulose derivatives (Polyquaternium-4 and -10), acrylamide copolymers(Polyquaternium-7).

Cationic guar derivatives such as guar hydroxypropyltrimonium chloride(INCI) can also be used.

Further suitable hair cosmetic polymers are also neutral polymers, suchas polyvinylpyrrolidones, copolymers of N-vinylpyrrolidone and vinylacetate and/or vinyl propionate, polysiloxanes, polyvinylcaprolactam andcopolymers containing N-vinylpyrrolidone, polyethyleneimines and saltsthereof, polyvinylamines and salts thereof, cellulose derivatives,polyaspartic acid salts and derivatives.

To set certain properties, the preparations may additionally alsocomprise conditioning substances based on silicone compounds. Suitablesilicone compounds are, for example, polyalkylsiloxanes,polyarylsiloxanes, polyarylalkylsiloxanes, polyether siloxanes, siliconeresins, or dimethicone copolyols (CTFA) and aminofunctional siliconecompounds such as amodimethicones (CTFA).

The polymers according to the invention are particularly suitable assetting agents in hair styling preparations, in particular hair sprays(aerosol sprays and pump sprays without propellant gas) and hair mousses(aerosol mousses and pump mousses without propellant gas).

In a preferred embodiment, these preparations comprise

-   a) 0.1 to 10% by weight of the polymer according to the invention-   b) 20 to 99.9% by weight of water and/or alcohol-   c) 0 to 70% by weight of a propellant-   d) 0 to 20% by weight of further constituents

Propellants are the propellants customarily used for hair sprays oraerosol mousses. Preference is given to mixtures of propane/butane,pentane, dimethyl ether, 1,1-difluoroethane (HFC-152 a), carbon dioxide,nitrogen or compressed air.

A formulation for aerosol hair mousses which is preferred according tothe invention comprises

-   a) 0.1 to 10% by weight of the polymer according to the invention-   b) 55 to 99.8% by weight of water and/or alcohol-   c) 5 to 20% by weight of a propellant-   d) 0.1 to 5% by weight of an emulsifier-   e) 0 to 10% by weight of further constituents

The emulsifiers used may be emulsifiers customarily used in hairmousses. Suitable emulsifiers may be nonionic, cationic or anionic oramphoteric.

Examples of nonionic emulsifiers (INCI nomenclature) are laureths, e.g.laureth-4; ceteths, e.g. ceteth-1, polyethylene glycol cetyl ether;ceteareths, e.g. ceteareth-25, polyglycol fatty acid glycerides,hydroxylated lecithin, lactyl esters of fatty acids, alkylpolyglycosides.

Examples of cationic emulsifiers arecetyldimethyl-2-hydroxyethylammonium dihydrogenphosphate, cetyltrimoniumchloride, cetyltrimonium bromide, cocotrimonium methylsulfate,Quaternium-1 to x (INCI).

Anionic emulsifiers may be chosen, for example, from the group of alkylsulfates, alkyl ether sulfates, alkylsulfonates, alkylarylsulfonates,alkyl succinates, alkyl sulfosuccinates, N-alkoyl sarcosinates, acyltaurates, acyl isethionates, alkyl phosphates, alkyl ether phosphates,alkyl ether carboxylates, alpha-olefinsulfonates, in particular thealkali metal and alkaline earth metal salts, e.g. sodium, potassium,magnesium, calcium, and ammonium and triethanolamine salts. The alkylether sulfates, alkyl ether phosphates and alkyl ether carboxylates canhave between 1 and 10 ethylene oxide or propylene oxide units,preferably 1 to 3 ethylene oxide units, in the molecule.

A preparation which is suitable according to the invention for stylinggels may, for example, have the following composition:

-   a) 0.1 to 10% by weight of the polymer according to the invention-   b) 60 to 99.85% by weight of water and/or alcohol-   c) 0.05 to 10% by weight of a gel former-   d) 0 to 20% by weight of further constituents

Gel formers which may be used are all gel formers customary incosmetics. These include slightly crosslinked polyacrylic acid, forexample Carbomer (INCI), cellulose derivatives, e.g.hydroxypropylcellulose, hydroxyethylcellulose, cationically modifiedcelluloses, polysaccharides, e.g. xanthum gum, caprylic/caprictriglycerides, sodium acrylates copolymer, polyquaternium-32 (and)paraffinum liquidum (INCI), sodium acrylates copolymer (and) paraffinumliquidum (and) PPG-1 trideceth-6, acrylamidopropyl trimoniumchloride/acrylamide copolymer, steareth-10 allyl ether acrylatescopolymer, polyquaternium-37 (and) paraffinum liquidum (and) PPG-1trideceth-6, polyquaternium 37 (and) propylene glycol dicapratedicaprylate (and) PPG-1 trideceth-6, polyquaternium-7,polyquaternium-44.

The polymers according to the invention can also be used in shampooformulations as setting agents and/or conditioning agents. Suitableconditioning agents are, in particular, polymers with a cationic charge.Preferred shampoo formulations comprise

-   a) 0.05 to 10% by weight of the polymer according to the invention-   b) 25 to 94.95% by weight of water-   c) 5 to 50% by weight of surfactant-   c) 0 to 5% by weight of a further conditioning agent-   d) 0-10% by weight of further cosmetic constituents

In the shampoo formulations, it is possible to use all anionic, neutral,amphoteric or cationic surfactants customarily used in shampoos.

Suitable anionic surfactants are, for example, alkyl sulfates, alkylether sulfates, alkylsulfonates, alkylarylsulfonates, alkyl succinates,alkyl sulfosuccinates, N-alkoylsarcosinates, acyl taurates, acylisethionates, alkyl phosphates, alkyl ether phosphates, alkyl ethercarboxylates, alpha-olefinsulfonates, in particular the alkali metal andalkaline earth metal salts, e.g. sodium, potassium, magnesium, calcium,and ammonium and triethanolamine salts. The alkyl ether sulfates, alkylether phosphates and alkyl ether carboxylates can have between 1 and 10ethylene oxide or propylene oxide units, preferably 1 to 3 ethyleneoxide units, in the molecule.

Suitable examples are sodium lauryl sulfate, ammonium lauryl sulfate,sodium lauryl ether sulfate, ammonium lauryl ether sulfate, sodiumlauroyl sarcosinate, sodium oleyl succinate, ammonium laurylsulfosuccinate, sodium dodecylbenzenesulfonate, triethanolaminedodecylbenzenesulfonate.

Suitable amphoteric surfactants are, for example, alkylbetaines,alkylamidopropylbetaines, alkylsulfobetaines, alkyl glycinates, alkylcarboxyglycinates, alkyl amphoacetates or amphopropionates, alkylamphodiacetates or amphodipropionates.

For example, it is possible to use cocodimethylsulfopropylbetaine,laurylbetaine, cocamidopropylbetaine or sodium cocamphopropionate.

Examples of suitable nonionic surfactants are the reaction products ofaliphatic alcohols or alkylphenols having 6 to 20 carbon atoms in thealkyl chain, which may be linear or branched, with ethylene oxide and/orpropylene oxide. The amount of alkylene oxide is about 6 to 60 mol permole of alcohol. Also suitable are alkylamine oxides, mono- ordialkylalkanolamides, fatty acid esters of polyethylene glycols, alkylpolyglycosides or sorbitan ether esters.

Furthermore, the shampoo formulations may comprise customary cationicsurfactants, such as, for example, quaternary ammonium compounds, forexample cetyltrimethylammonium chloride.

In the shampoo formulations, to achieve certain effects, customaryconditioning agents may be used in combination with the polymersaccording to the invention. These include, for example, cationicpolymers with the INCI name Polyquaternium, in particular copolymers ofvinylpyrrolidone/N-vinylimidazolium salts (Luviquat® FC, Luviquat® HM,Luviquat® MS, Luviquat® Care), copolymers ofN-vinylpyrrolidone/dimethylaminoethyl methacrylate, quaternized withdiethyl sulfate (Luviquat® PQ 11), copolymers ofN-vinylcaprolactam/N-vinylpyrrolidone/N-vinylimidazolium salts(Luviquat® Hold); cationic cellulose derivatives (Polyquaternium-4, and-10), acrylamide copolymers (Polyquaternium-7). It is also possible touse protein hydrolysates, and conditioning substances based on siliconecompounds, for example polyalkylsiloxanes, polyarylsiloxanes,polyarylalkylsiloxanes, polyethersiloxanes or silicone resins. Furthersuitable silicone compounds are dimethicone copolyols (CTFA) andaminofunctional silicone compounds such as amodimethicones (CTFA). It isalso possible to use cationic guar derivatives, such as guarhydroxypropyltrimonium chloride (INCI).

The examples below serve to further illustrate the invention.

A Preparation of the Polymer

EXAMPLE 1 Water-in-Water Emulsion Polymerization of VP and Quat-311 inthe Presence of a Mixture of Na₂SO₄ and NaCl

Sodium sulfate (50 g) and sodium chloride (30 g), vinylpyrrolidone (128g), quat-311 (64 g, 50% by weight solution in water) and 0.35 g ofbutanediol diacrylate were dissolved in water (347 g). As protectivecolloid, 63 g of poly(vinylamine-co-acrylic acid=3:7) (25% by weightsolution in water) were added. The pH was adjusted to a value of 6.75using 50% sulfuric acid, and the emulsion obtained was flushed withnitrogen for about 10 minutes. The free radical initiator(2,2′-azobis(2-amidinopropane)dihydrochloride: V-50; 0.48 g) was thenadded and the reaction mixture was heated to 60° C. under a nitrogenatmosphere. After the reaction mixture had been stirred at thistemperature for 3 hours, a second portion of V-50 (0.96 g) was added andthe mixture was stirred for a further 3 hours at 70° C. and then cooledto room temperature. This gave a white suspension with a polymer contentof 23% and a viscosity of 1650 mPas. Dilution of the emulsion with waterto 6.5% by weight gave a clear solution of 8000 mPas.

EXAMPLE 2 Water-in-Water Emulsion Polymerization of VP and QVI in thePresence of Na₂SO₄

Sodium sulfate (77 g), vinylpyrrolidone (128 g), quaternisedvinylimidazolium (64 g, 50% by weight solution in water) and 0.48 g oftriallylamine were dissolved in water (347 g). As protective colloid, 63g of poly(vinylamine-co-acrylic acid)=1:9) (25% by weight solution inwater) were added. The pH was adjusted to a value of 6.75 using 50%sulfuric acid, and the emulsion obtained was flushed with nitrogen forabout 10 minutes. The free radical initiator (V-50; 0.48 g) was thenadded and the reaction mixture was heated to 60° C. under a nitrogenatmosphere. After the reaction mixture had been stirred at thistemperature for 3 hours, a second portion of V-50 (0.96 g) was added,and the mixture was stirred for a further 3 hours at 70° C. and thencooled to room temperature. This gave a white suspension with a polymercontent of 23% and a viscosity of 1100 mPa·s. Dilution of the emulsionwith water to 6.5% by weight gave a clear solution of 11 500 mPas.

EXAMPLE 3 Water-in-Water Emulsion Polymerization of VP and QVI in thePresence of a Mixture of Na₂SO₄ and (NH₄)₂SO₄

Sodium sulfate (65 g) and ammonium sulfate (30 g), vinylpyrrolidone (128g), quaternized vinylimidazolium (64 g, 45% by weight solution in water)and 0.25 g of triallylamine were dissolved in water (347 g). Asprotective colloid, 63 g of polyacrylic acid (Sokalan HP80 25% by weightsolution in water) were added. The pH was adjusted to a value of 6.75using 50% sulfuric acid and the emulsion obtained was flushed withnitrogen for about 10 minutes. The free radical initiator (V-44; 0.48 g)was then added and the reaction mixture was heated to 60° C. under anitrogen atmosphere. After the reaction mixture had been stirred at thistemperature for 3 hours, a second portion of V-50 (0.96 g) was added andthe mixture was stirred for a further 3 hours at 70° C. and then cooledto room temperature. This gave a white suspension with a polymer contentof 23% and a viscosity of <1000 mPas. Dilution of the emulsion withwater to 6.5% by weight gave a clear solution of 4500 mPas.

EXAMPLE 4 (COMPARATIVE EXPERIMENT TO EXAMPLE 2) Solution Polymerizationof VP and QVI

Vinylpyrrolidone (128 g), quaternized vinylimidazolium (64 g, 50% byweight solution in water) and 0.75 g of triallylamine were dissolved inwater (347 g). The pH was adjusted to a value of 6.75 using 50% sulfuricacid and the emulsion obtained was flushed with nitrogen for about 10minutes. The free radical initiator (V-50; 0.48 g in 200 g of water) wasthen added and the reaction mixture was heated to 65° C. under anitrogen atmosphere. After the reaction mixture had been stirred at thistemperature for 3 hours, a second portion of V-50 (0.96 g in 250 g ofwater) was added and the mixture was stirred for a further 3 hours at70° C. and then cooled to room temperature. After the polymerization,800 g of water were added in order to adjust the concentration to 6.5%by weight. This gave a clear solution with a polymer content of 6.5% anda viscosity of 6050 mPas.

EXAMPLE 5 (COMPARATIVE EXPERIMENT TO EXAMPLE 3) Solution Polymerizationof VP and QVI

Sodium sulfate (77 g), vinylpyrrolidone (128 g), quaternizedvinylimidazolium (64 g, 45% by weight solution in water) and 0.25 g oftriallylamine were dissolved in water (500 g). The pH was adjusted to avalue of 6.75 using 50% sulfuric acid and the emulsion obtained wasflushed with nitrogen for about 10 minutes. The free radical initiator(V-50; 0.48 g in 100 g of water) was then added and the reaction mixturewas heated to 65° C. under a nitrogen atmosphere. After the reactionmixture had been stirred at this temperature for 3 hours, a secondportion of V-50 (0.96 g in 100 g of water) was added and the mixture wasstirred for a further 3 hours at 70° C. and then cooled to roomtemperature. This gave a clear solution with a polymer content of 22.8%and a viscosity of >16 500 mPas. The polymer comprised large amounts ofinsoluble solid particles and dilution of the solution with water to6.5% by weight gave a solution of 1100 mPas with solid insolubleparticles. TABLE 1 Summary of experiments 1 to 6 Tel Quel. viscositySolution viscosity Appearance Example (mPas/% by wt.) (mPas/6.5% by wt.)of solution 1 1650/23/emulsion 8000/solution clear/no structure 21100/23/emulsion 11500/solution clear/no structure 3 <500/23/emulsion4500/solution clear/no structure 4 950/6.5/solution 950/solutionclear/slight struc- ture 5 16400/23/solution 1100/solutionclear/structure

The polymers to be used according to the invention have, as aqueoussolutions at 6.5% by weight, higher solution viscosities (compareexample 1 to 3 and example 4 to 5).

The polymers can be prepared as dispersions with a relatively highsolids content (23% by weight) and a low viscosity. The 23% by weightsolution of polymer is not readily pumpable and has many gel particles,but in the form of a dispersion it can be handled easily (compareexample 3 and example 5).

The polymeric solutions at 6.5% by weight exhibit, as solution polymer,a flow structure which is produced by the gel particles, but thesolutions of the dispersions according to the invention exhibit nostructure.

B Use of the Dispersions According to the Invention as Conditioners

For the performance investigation, the polymers were used in asurfactant solution formulation with the following composition:

-   40.0% of Texapon NSO (sodium laureth sulfate solution 28%; Cognis)-   10.0% of Tego-Betaine L7 (cocamidopropylbetaine solution 30%;    Goldschmidt)-   0.5% of polymer (solids content) ad 100% of water    I) Determination of the Combability

The following instructions describe the procedure for determining thewet and dry combability of hair following treatment with conditioningagents. All measurements were carried out in a climatically controlledroom at 65% relative humidity and 21° C.

Instruments Used

Wet combability: Frank tensile/force tester

Dry combability: Diastron force measuring system

Digital balance: (top-pan balance)

Hair:

-   a) European, bleached: hair tresses from Wernesgrün (bleaching see    below)-   b) Asiatic, untreated: hair tresses from Wernesgrün with split ends

The following tests were carried out:

-   -   wet combability following application of shampoo on European,        bleached hair    -   dry combability following application of shampoo on Asiatic hair        Pretreatment/Cleansing of the Hair:

Prior to the first use, the Asiatic hair tresses were cleansed in asolvent mixture (ethanol/isopropanol/acetone/water 1:1:1:1) until thehair appeared clean in the dry state (i.e. no longer stuck together).The hair was then washed with sodium lauryl ether sulfate.

The European hair was then treated with a bleaching paste (7.00 g ofammonium carbonate, 8.00 g of calcium carbonate, 0.50 g of Aerosil 200,9.80 g of hydrogen peroxide (30% strength), 9.80 g of demineralizedwater). The hair tresses were completely immersed in the bleaching pasteto ensure extensive wetting of the entire surface of the hair. Thetresses were then wiped between the fingers in order to remove excessbleaching paste. The contact time of the remaining bleach on the hair ismatched to the degree of damage required, and is generally 15 to 30minutes, but can vary depending on the quality of the hair. The bleachedhair tresses were then thoroughly rinsed under running tap water (2minutes) and washed with sodium lauryl ether sulfate. The hair was thendipped briefly into an aqueous acidic solution (e.g. citric acid)because of so-called insidious bleaching, and then rinsed with tapwater.

Applications:

The hair tress is dipped for one minute into the surfactant formulationto be tested, shampooed for one minute and then rinsed for one minuteunder running drinking water (hand-hot).

I) Wet Combability

Determination of the blank value for wet combability: the washed hairwas dried overnight in a climatically controlled room. Prior tomeasurement, it was shampooed twice with Texapon NSO for a total of oneminute and rinsed for one minute so that it is definitely wet, i.e.swollen. Prior to the start of the measurement, the tress was precombeduntil the knots were no longer present in the hair and thus a constantapplication of force is necessary for the repeated measurement combing.The tress was then fixed to the support and combed using thefinely-toothed side of the comb into the finely-toothed side of the testcomb. The hair was inserted into the test comb for each measurementuniformly and without tension. The measurement was started and evaluatedby means of software (EGRANUDO program, Frank). The individualmeasurement was repeated 5 to 10 times. The calculated average value wasnoted.

Determination of the measurement value for wet combability: Followingthe determination of the blank value, the hair was treated depending onthe desired application. The combing force is measured analogously tothe blank-value determination.

Evaluation:Reduction in combing force wet [%]=100−(measurement value*100/blankvalue)II) Dry Combability

Determination of the blank value for dry combability: the washed hairwas dried overnight in a climatically controlled room. Prior to thestart of the measurement, the tress was precombed until knots were nolonger present in the hair and thus a constant application of force isnecessary for repeated measurement combing. The tress was then fixed tothe support and combed into the finely-toothed side of the test comb.The hair was inserted into the test comb for each measurement uniformlyand without tension. The measurement was started and evaluated by meansof software (mtt-win, DIASTRON). The individual measurement was repeated5 to 10 times. The calculated average value was noted together with thestandard deviation.

Determination of the measurement value for dry combability: followingthe determination of the blank value, the hair was treated according tothe desired application and dried overnight. The combing force wasmeasured analogously to the blank-value determination. Evaluation:Reduction in combing force dry [%]=100−(measurement value*100/blankvalue)

The results are summarized in table 2. TABLE 2 Performance tests withthe above mentioned test shampoo Reduction in Reduction in combingcombing Appearance Shampoo Preparation force, wet force, dry of shampooexample No. example No. (Grade/%) (Grade/%) solution 6 1 1-2/53 1-2/85clear 7 2 1-2/56 1-2/79 clear 8 3 1-2/48  1-/88 clear 9 4  2+/18   2/48clear 10  5  2+/29 2-3/45 clear

Examples 6 to 8 clearly show the excellent properties in the case of theuse according to the invention (examples 6 to 8) compared with the knownprocess variant (example 9 to 10). In comparison with this, polymerswhich are not prepared in the presence of salt do not produce goodperformance properties. Polymers which are prepared as water-in-wateremulsion polymers in the presence of salt exhibit very good performanceproperties.

A further advantage is that clear formulations are also possible withthe polymer according to the invention.

EXAMPLE 11 Water-in-Water Emulsion Polymerization of VP, VFA, and QVI inthe Presence of Na₂SO₄

Sodium sulfate (77 g), vinylpyrrolidone (80 g), vinylformamide (48 g),quaternized vinylimidazolium (64 g, 50% by weight solution in water) and0.6 g of triallylamine were dissolved in water (347 g). As protectivecolloid, 63 g of poly(vinylamine-co-acrylic acid)=1:9) (25% by weightsolution in water) were added. The pH was adjusted to a value of 6.75using 50% sulfuric acid and the emulsion obtained was flushed withnitrogen for about 10 minutes. The free radical initiator (V-50; 0.48 g)was then added and the reaction mixture was heated to 60° C. under anitrogen atmosphere. After the reaction mixture had been stirred at thistemperature for 3 hours, a second portion of V-50 (0.96 g) was added andthe mixture was stirred for a further 3 hours at 70° C. and then cooledto room temperature. This gave a white suspension with a polymer contentof 23% and a viscosity of 2300 mPas. Dilution of the emulsion with waterto 6.5% by weight gave a clear solution of 7500 mPas.

EXAMPLE 12 Water-in-Water Emulsion Polymerization of VP, VCap, and QVIin the Presence of Na₂SO₄

Sodium sulfate (77 g), vinylpyrrolidone (88 g), vinylcaprolactam (40 g),quaternized vinylimidazolium (64 g, 50% by weight solution in water) and0.6 g of triallylamine were dissolved in water (297 g). As protectivecolloid, 63 g of poly(vinylamine-co-acrylic acid)=1:9) (25% by weightsolution in water) were added. The pH was adjusted to a value of 6.75using 50% sulfuric acid and the emulsion obtained was flushed withnitrogen for about 10 minutes. The free radical initiator (V-50; 0.48 gin 50 ml of water) was then added over 3 hours and the reaction mixturewas heated to 65° C. under a nitrogen atmosphere. After the reactionmixture had been stirred at this temperature for 3 hours, a secondportion of V-50 (0.96 g) was added, and the mixture was stirred for afurther 3 hours at 70° C. and then cooled to room temperature. This gavea white suspension with a polymer content of 23% and a viscosity of 2300mPas. Dilution of the emulsion with water to 6.5% by weight gave a clearsolution of 7500 mPas.

EXAMPLE 13 Water-in-Water Emulsion Polymerization of VP, VCap, and QVIin the Presence of NaCl and Na₂SO₄

Sodium sulfate (60 g), sodium chloride (20 g), vinylpyrrolidone (128 g),quaternized vinylimidazolium (64 g, 50% by weight solution in water) and0.6 g of triallylamine were dissolved in water (347 g). As protectivecolloid, 63 g of poly(vinylamine-co-acrylic acid)=1:9) (25% by weightsolution in water) were added. The pH was adjusted to a value of 6.75using 50% sulfuric acid, and the emulsion obtained was flushed withnitrogen for about 10 minutes. The free radical initiator (V-50; 0.48 g)was then added and the reaction mixture was heated to 60° C. under anitrogen atmosphere. After the reaction mixture had been stirred at thistemperature for 3 hours, a second portion of V-50 (0.96 g) was added andthe mixture stirred for a further 3 hours at 70° C. and then cooled toroom temperature. This gave a white suspension with a polymer content of23% and a viscosity of 2300 mPas. Dilution of the emulsion with water to6.5% by weight gave a clear solution of 7500 mPas. Example 14: Clearconditioner shampoo % Ingredient INCI 15.00  Tego Betaine L 7Cocamidopropylbetaine 10.00  Amphoteric surfactant GB 2009 Disodiumcocoamphodiacetate 5.00 Cremophor PS 20 Polysorbate 20 5.00 Plantacare2000 Decyl glucoside 3.00 Stepan PEG 6000 DS PEG-150 distearate q.s.Perfume q.s. Preservative q.s. Citric acid 0.1-1.0 Active substance ofconditioner polymer as in Example 1 2.00 Rewopal LA 3 Laureth-3 ad 100Water, demineralized Aqua dem. Example 15: Conditioner shampoo %Ingredient INCI 30.00  Texapon NSO Sodium laureth sulfate 6.00 Dehyton GSodium cocoamphoacetate 6.00 Dehyton K Cocamidopropylbetaine 3.00Euperlan PK 771 Sodium laureth sulfate, glycol distearate, cocamide MEA,laureth-10 0.1-1.0 Active substance of conditioner polymer as in Example1 2.00 Dimethicone q.s. Perfume q.s. Preservative q.s. Citric acid 1.00Sodium chloride ad 100 Water, demineralized Aqua dem. Example 16:Conditioner shampoo % Ingredient INCI 30.00  Texapon NSO Sodium laurethsulfate 6.00 Dehyton G Sodium cocoamphoacetate 6.00 Dehyton KCocamidopropylbetaine 3.00 Euperlan PK 771 Sodium laureth sulfate,glycol distearate, cocamide MEA, laureth-10 0.1-1.0 Active substance ofconditioner polymer as in Example 2 2.00 Amidodimethicone q.s. Perfumeq.s. Preservative q.s. Citric acid 1.00 Sodium chloride ad 100 Water,demineralized Aqua dem. Example 17: Conditioner shampoo % IngredientINCI 40.00  Texapon NSO Sodium laureth sulfate 10.00  Dehyton KCocamidopropylbetaine 3.00 Euperlan PK 771 Sodium laureth sulfate,glycol distearate, cocamide MEA, laureth-10 0.1-1.0 Active substance ofconditioner polymer as in Example 2 2.00 Dow Corning 3052 q.s. Perfumeq.s. Preservative q.s. Citric acid 2.00 Cocamido DEA ad 100 Water,demineralized Aqua dem. Example 18: Conditioner Shampoo % IngredientINCI 30.00  Texapon NSO Sodium laureth sulfate 6.00 Dehyton G Sodiumcocoamphoacetate 6.00 Dehyton K Cocamidopropylbetaine 3.00 Euperlan PK771 Sodium laureth sulfate, glycol distearate, cocamide MEA, laureth-100.1-1.0 Active substance of conditioner polymer as in Example 2 2.00Dimethicone q.s. Perfume q.s. Preservative q.s. Citric acid 2.00Cocamido DEA ad 100 Water, demineralized Aqua dem. Example 19:Anti-dandruff shampoo % Ingredient INCI 40.00  Texapon NSO Sodiumlaureth sulfate 10.00  Tego Betaine L 7 Cocamidopropylbetaine 10.00 Rewopol SB FA 30 Disodium laureth sulfo- succinate 2.50 Euperlan PK 771Sodium laureth sulfate, glycol distearate, cocamide MEA, laureth-100.1-1.0 Active substance of conditioner polymer as in Example 3 0.50Crinipan AD Climbazole q.s. Perfume q.s. Preservative q.s. Citric acid0.50 Sodium chloride ad 100 Water, demineralized Aqua dem. Example 20:Shampoo % Ingredient INCI 25.00  Sodium laureth sulfate 5.00Cocamidopropylbetaine 2.50 Euperlan PK 771 Sodium laureth sulfate,glycol distearate, cocamide MEA, laureth-10 0.1-1.0 Active substance ofconditioner polymer as in Example 3 2.0  Cocamido DEA q.s. Perfume q.s.Preservative ad 100 Water, demineralized Aqua dem. Example 21: Shampoo %Ingredient INCI 20.00  Ammonium laureth sulfate 15.00  Ammonium laurylsulfate 5.00 Cocamidopropylbetaine 2.50 Euperlan PK 771 Sodium laurethsulfate, glycol distearate, cocamide MEA, laureth-10 0.1-1.0 Activesubstance of conditioner polymer as in Example 3 q.s. Perfume q.s.Preservative 0.50 Sodium chloride ad 100 Water, demineralized Aqua dem.Example 22: Shampoo % Ingredient INCI 20.00  Sodium laureth sulfate15.00  Sodium lauryl sulfate 5.00 Cocamidopropylbetaine 2.50 Euperlan PK771 Sodium laureth sulfate, glycol distearate, cocamide MEA, laureth-100.1-1.0 Active substance of conditioner polymer as in Example 2 q.s.Perfume q.s. Preservative 0.50 Sodium chloride ad 100 Water,demineralized Aqua dem. Example 23: Clear shower gel % Ingredient INCI40.00  Texapon NSO Sodium laureth sulfate 5.00 Plantacare 2000 Decylglucoside 5.00 Tego Betaine L 7 Cocamidopropylbetaine 0.1-1.0 Activesubstance of conditioner polymer as in Example 2 1.00 D-Panthenol USPPanthenol q.s. Perfume q.s. Preservative q.s. Citric acid 2.00 Sodiumchloride ad 100 Water, demineralized Aqua dem. Example 24: Shampoo %Ingredient INCI 12.00  Texapon N 70 Sodium laureth sulfate 1.50Plantacare 2000 Decyl glucoside 2.50 Dehyton PK 45 Cocamidopropylbetaine5.00 Lamesoft PO 65 Cocoglucoside glyceryl oleate 2.00 Euperlan PK 771Sodium laureth sulfate, glycol distearate, cocamide MEA, Laureth-100.1-1.0 Active substance of conditioner polymer as in Example 1 q.s.Preservative q.s. Sicovit Sunset Sunset Yellow C. I. 15 985 Yellow 85 E110 q.s. Perfume 1.00 Sodium chloride ad 100 Water, demineralizedExample 25: Shampoo % Ingredient INCI 12.00  Texapon N 70 Sodium laurethsulfate 1.50 Plantacare 2000 Decyl glucoside 2.50 Dehyton PK 45Cocamidopropylbetaine 5.00 Lamesoft PO 65 Cocoglucoside glyceryl oleate2.00 Euperlan PK 771 Sodium laureth sulfate, glycol distearate, cocamideMEA, Laureth-10 0.1-1.0 Active substance of conditioner polymer as inExample 1 q.s. Preservative q.s. Sicovit Sunset Sunset Yellow C. I. 15985 Yellow 85 E 110 q.s. Perfume 1.00 Sodium chloride ad 100 Water,demineralized

1. The use of crosslinked cationic polymers preparable by polymerizationof a) 1 to 99.9% by weight, based on the total amount of monomers usedfor the preparation of the polymer, of at least one cationic orcationogenic vinyl group-containing monomer chosen from the groupconsisting of N-vinylimidazoles, diallylamines,dialkylaminoalkyl(meth)acrylamides anddialkylaminoalkyl(meth)acrylamides and dialkylaminoalkyl(meth)acrylates, b) 0 to 99% by weight, based on the total amount ofmonomers used for the preparation of the polymer, of at least oneneutral or basic water-soluble monomer different from (a), c) 0 to 50%by weight, based on the total amount of monomers used for thepreparation of the polymer, of at least one unsaturated acid or oneunsaturated anhydride, d) 0 to 50% by weight of at least onefree-radically copolymerizable monomer different from (a), (b) or (c);and e) 0.05 to 10% by weight, based on the total amount of monomers usedfor the preparation of the polymer, of at least one crosslinking monomerwith at least two ethylenically unsaturated, nonconjugated double bonds,where the amounts a) to e) are chosen such that the resulting polymer,optionally after quaternization or protonation, has an overall positivecharge, in water in the presence of f) 1 to 100% by weight of thesaturation amount in the reaction medium of one or more organic orinorganic salts, and g) 0.1 to 30% by weight, based on the total weightof the dispersion, of at least one water-soluble protective colloid witha composition different from a) to e), and subsequent at least partialquaternization for cases where the monomer (a) is not quaternized, incosmetics.
 2. The use as claimed in claim 1 in hair cosmetics.
 3. Theuse as claimed in claim 1, wherein the free-radically polymerizablevinyl group-containing cationic monomer used is at least oneN-vinylimidazole derivative of the formula (I),

in which the radicals R¹ to R³, independently of one another, arehydrogen, C₁-C₄-alkyl or phenyl.
 4. The use as claimed in claim 1,wherein the free-radically polymerizable vinyl group-containing cationicmonomer used is at least one diallylamine derivative of the formula(II),

in which the radical R⁴ is C₁-C₂₄-alkyl.
 5. The use as claimed in claim1, wherein the free-radically polymerizable vinyl group-containingcationic monomer used is at least one dialkylaminoalkyl(meth)acrylamideand dialkylaminoalkyl (meth)acrylate of the formula (III),

in which R⁵ and R⁶, independently of one another, are hydrogen ormethyl, Z is a nitrogen atom where x=1 or an oxygen atom where x=0, R⁷is a linear or branched C₁-C₂₄-alkylene radical, and R⁸ and R⁹,independently of one another, are a C₁-C₂₄-alkylene radical.
 6. The useas claimed in claim 1, where the monomer (b) used is at least oneN-vinyllactam.
 7. The use as claimed in claim 1 as conditioning agent orthickener.